JP3537937B2 - Hydrodesulfurization catalyst for gas oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a gas oil hydrodesulfurization catalyst capable of effectively removing sulfur compounds which are difficult to desulfurize in a deep desulfurization region, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Hydrocarbon oils generally contain sulfur compounds, and when those oils are used as fuel, the sulfur present in the sulfur compounds is converted to sulfur oxides and emitted to the atmosphere. Therefore, taking into account the air pollution when burning,
It is desirable that the sulfur content in the hydrocarbon oil be as low as possible. Reduction of sulfur content can be achieved by catalytic hydrodesulfurization of hydrocarbon oils.

In addition, due to environmental problems, regulations on sulfur contained in commercial diesel oil are becoming stricter (the conventional 0.2 watts).
t% to 0.05 wt%), further depth desulfurization is required, and 4-MDBT (4 methyldibenzothiophene) and 4,6- There is a need for treatment of non-desulfurizable substances centered on DMDBT (4,6 dimethyldibenzothiophene).

[0004] Catalysts used in such hydrodesulfurization intended for deep desulfurization include metals of Group VI (hereinafter referred to as "Group 6") of the periodic table and Group VIII (hereinafter referred to as "Group 6") of the periodic table. Group 8) is a catalyst comprising a metal as an active metal and supported on an oxide carrier such as alumina, magnesia, and silica;
Generally, Mo is used as the Group 6 metal, and Co or Ni is used as the Group 8 metal.

Further, in order to improve the activity of hydrodesulfurization and hydrocracking of heavy oil using this catalyst, that is, a CoMo-based or NiMo-based catalyst, the addition of phosphorus, boron, and the like has been reported (Japanese Patent Laid-Open No. 52-1982). 13503).

Further, a technique has been reported in which tungsten is mixed in a combined catalyst of Group 6 and Group 8 for hydrodesulfurization of a hydrocarbon oil (Applied Data).
lysis A: General 109 (1994)
195-210). However, this technique is mainly intended for desulfurization of heavy oil, but not for deep desulfurization of light oil and desulfurization of hardly desulfurizable substances.

[0007] In addition, the present inventors have disclosed in Japanese Patent Application No. 7-168.
296 reports that a certain level of desulfurization can be achieved in gas oil desulfurization by using a CoMoW-based or NiMoW-based catalyst. Based on this technique, it is desired to provide a catalyst having a higher desulfurization activity from the viewpoint of reducing the amount of catalyst in an actual apparatus, relaxing reaction conditions, and the like.

[0008]

An object of the present invention is to meet the above-mentioned demands and to have a more excellent desulfurization activity in the deep desulfurization region.
It is an object of the present invention to provide a hydrodesulfurization catalyst for gas oil.

[0009]

SUMMARY OF THE INVENTION The present inventors have conducted various studies to achieve the above object, and as a result, have found that tungsten and phosphorus (hereinafter, referred to as tungsten and phosphorus).
Focusing on the fact that "W" and "P" are sometimes carried out in the same catalyst, thereby exerting an effect on hydrodesulfurization of a non-desulfurizable sulfur compound, (1) P First, Mo and W are supported on the supported carrier at a fixed ratio,
After that, either or both of Co and Ni were supported, or (2) P was simultaneously impregnated and supported with Mo, W, and / or Co and / or Ni at a certain ratio, and (3) It has been found that those having a specific average pore diameter can also effectively remove hard-to-desulfurize sulfur compounds in the deep desulfurization region.

[0010] The present invention is based on the above-mentioned findings, and based on the catalyst, 1 to 10% by mass of cobalt and / or nickel is converted to oxide on an inorganic oxide carrier. Tungsten is supported so that phosphorus is 1 to 5% by mass in terms of oxide, molybdenum is 10 to 25% by mass in terms of oxide, and the mass ratio of tungsten to molybdenum is 0.01 to 0.2 in terms of oxide. and and an average pore diameter of the catalyst I is 70 to 80 Å der, [1] the inorganic oxide support, carrying the phosphorus in the first stage
And the second stage carries molybdenum and tungsten, and the third stage
Cobalt and / or nickel by eye
Or (2) cobalt and nickel on the above-mentioned inorganic oxide carrier.
And / or molybdenum or tungsten
Emissions, phosphorus ing carrying simultaneously in one step, and the gist of hydrodesulfurization catalysts in gas oil, characterized in that.

In the present invention, the carrier of the catalyst is a crystalline inorganic oxide. Various inorganic oxides can be used, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-
Berylia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica- Magnesia-zirconia, etc., which may be used alone or
More than one species can be used in combination.

Among these inorganic oxides, preferred are alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, with γ-alumina being particularly preferred.

The above-mentioned carrier (or the catalyst of the present invention comprising the above-mentioned carrier) includes montmorillonite, kaolin,
One or more clay minerals such as halosite, bentonite, adavalguite, bauxite, kaolinite, nacrite, and anoxite may be contained.

The specific surface area of the support made of these inorganic oxides is not particularly limited, but is 250 m ² / g.
The above is preferable. The pore volume of the carrier is also not particularly limited, but is preferably 0.4 to 1.2 cc / g. The average pore diameter of the carrier is not particularly limited, either.
It is preferable to use those having a temperature of 0 to 130 °.

The catalyst of the present invention is obtained by supporting a specific amount of cobalt and / or nickel, molybdenum, tungsten and phosphorus on the above-mentioned carrier.

The supported amount of cobalt and / or nickel is 1 to 1 in terms of oxide on a catalyst basis.
It is 10% by mass, preferably 3 to 7% by mass. 1% by mass of cobalt and / or nickel
If less than 10% by mass, no hydrodesulfurization activity is exhibited.
Even if it is more, the improvement of the activity corresponding to it cannot be obtained,
Economically disadvantaged.

The supported amount of phosphorus is 1 to 5% by mass, preferably 1.5 to 3% by mass in terms of oxide on a catalyst basis.
If the amount of phosphorus is too small, the tungsten cannot be effectively dispersed in a high degree. If the amount is too large, the pore volume of the prepared catalyst tends to be too small, and the catalytic activity tends to decrease.

The amount of molybdenum supported is 10 to 25% by mass, preferably 15 to 20% by mass. If the amount of molybdenum is less than 10% by mass, the absolute amount of molybdenum acting as an active site becomes too small to exhibit hydrodesulfurization activity. If the amount is more than 25% by mass, aggregation of metal molybdenum occurs, and conversely, the active site , The hydrodesulfurization activity decreases.

The amount of tungsten supported is such that the mass ratio of tungsten to molybdenum is WO ₃ : MoO ₃ =
0.01: 1 to 0.20: 1, preferably 0.02: 1
~ 0.1: 1, more preferably 0.04: 1 ~ 0.0
The amount is set to be 7: 1. When the mass ratio of WO ₃ to MoO ₃ (hereinafter, simply referred to as “ratio”) is less than 0.01, the above-mentioned nuclear hydrogenation activity of the non-desulfurizable substance is not exhibited,
If it is more than 0.2, the amount of tungsten to be supported is too large, and even if phosphorus is supported near the upper limit of the range of the supported amount, agglomeration of metal tungsten occurs, which is the same as the case of molybdenum. Similarly, the number of active sites is reduced, and the efficiency of removing hard-to-desulfurize substances in hydrodesulfurization is reduced.

In the catalyst of the present invention, the specific surface area and the pore volume are not particularly limited as long as they can function as a catalyst. Preferably, the pore volume is 200 m ² / g or more and the pore volume is 0.4 to 1.2 cc / g.

The average pore diameter is in the range of 70 to 80 °. If the average pore diameter is less than 70 °, the reactants are difficult to diffuse into the pores, so that the nuclear hydrogenation reaction of the non-desulfurizable substance does not effectively occur, and the physical properties required for functioning as a catalyst In order to obtain (specific surface area, pore volume), difficult problems such as insufficient mechanical strength occur.

When the angle is larger than 80 °, although the diffusibility of the reactant into the pores is good, the effective surface area of the catalyst is small, so that it is also difficult to remove the hardly desulfurizable substance. More specifically, when performing a deep desulfurization reaction, it is important to reduce the sulfur content to a predetermined level or less without deteriorating the hue of the produced gas oil, and therefore, it is necessary to perform an operation with a low liquid hourly space velocity. Many. In this case, the contact time becomes longer, so that it is not necessary to use a catalyst having an average pore size of more than 80 ° to improve the diffusibility of the reactant, and conversely, to use a catalyst having an average pore size of more than 90 °. When using, the contact effect between the reactant diffused in the pores and the reaction surface is reduced, and no improvement in activity is observed.

The pore size distribution of the catalyst (ie, the ratio of pores having a pore size of average pore size ± 15 °) is 70%.
% Or more, preferably 80% or more. If the pore size distribution value is small and the distribution curve is broad, even if the average pore size is an ideal value, the number of effective pores for the reaction will be relatively small, and a highly active catalyst Can not expect.

[0024] The catalyst of the present invention described above, you detailed below
Be those produced by Methods are particularly highly dispersed tungsten, by extension important in obtaining high activity of the catalyst
There is .

That is, each component is added to the above-mentioned carrier,
(1) Loading in a specific order (that is, phosphorus is supported in the first stage, molybdenum and tungsten are supported in the second stage, and
Stage carrying cobalt and one or both either nickel) makes method (hereinafter, "(1) Method" and referred) to or by, or (2) the method for supporting at a time (hereinafter, "(2) is due to referred to as the method ").

In the present invention, the above-mentioned method for supporting each component is as follows.
The impregnation method is adopted, in the method of (1), the compounds of the components in each impregnation of the solution of each performs dried and fired. Specifically, the first stage is impregnated with a solution of phosphorus, dried and calcined, then the second stage is impregnated with a solution of molybdenum and tungsten, dried and calcined, and the third stage is a mixture of both cobalt and nickel. Alternatively, one of the solutions is impregnated, and dried and fired. In the method (2), a solution in which the above components are dissolved is impregnated, dried, and fired.

In the impregnation sequence of the above method (1), when the phosphorus impregnation is at the second or third stage, phosphorus is selectively applied to the catalytically active sites on molybdenum, tungsten, cobalt or nickel already supported. Adsorbed on
Not only can tungsten not be highly dispersed by phosphorus, but rather a catalyst with low activity. Therefore,
It is important that phosphorus be impregnated in the first stage or simultaneously with these components to achieve high dispersion of tungsten by phosphorus and exhibit a highly active catalytic action.

In the compound of each component described above, various salts can be used as the compound of cobalt or nickel, and examples thereof include carbonate, acetate, nitrate, lead sulfate, and phosphate. Alone or 2
More than one species can be used in combination.

Examples of the phosphorus compound include orthophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid and polyphosphoric acid. These phosphoric acids can be used alone or in combination of two or more. Preferably, orthophosphoric acid is used.

Examples of the compounds of molybdenum, there can be used various ones, for _{example, (NH 4) 6 Mo 7} O 24 · 4H
Ammonium molybdate represented by ₂ O, H ₃ (PM
molybdophosphoric acid represented by o ₁₂ O ₄₀ ) · 30H ₂ O, molybdenum oxide represented by MoO ₃ , and the like.
These can be used alone or in combination of two or more.

Various tungsten compounds can be used, for example, 5 (NH ₄ ) ₂ O · 12WO ₃
· 11H ammonium paratungstate represented by _{2 O, (NH 4) 2} W 4 O ammonium metatungstate represented by 13 · 8H _{2 O,} tungstic acid represented by _{H 2 WO 4, H 3 (} PW Tungstophosphoric acid represented by ₁₂ O ₄₀ ) · 30H ₂ O and the like can be used, and these can be used alone or in combination of two or more.

The amount of each of the molybdenum, tungsten, cobalt or nickel and phosphorus dissolved in the impregnating solution (that is, the concentration of each component in each solution) is not particularly limited. In consideration of the easiness of the operation, the amount of the solvent in each of these impregnation operations is suitably 50 to 150 g, preferably 70 to 90 g, based on 100 g of the carrier.
In consideration of the amount of the solvent, the ratio of each component to the catalyst after the calcination may be set so as to be the above-described amount in terms of oxide.

The impregnation conditions for impregnating each of the above solutions are not particularly limited, but usually, in each of the steps of the above method (1) and the method of (2), the temperature is from 10 to 10.
100 ° C., preferably 10 to 50 ° C., more preferably 15 to 30 ° C., and the time is 15 minutes to 3 hours, preferably 20 minutes to 2 hours, more preferably 30 minutes to 1 hour. Is suitable. At this time, it is preferable to involve stirring.

In each of the steps (1) and (2), drying and firing are performed as follows. Drying can be performed by various drying methods such as air drying, hot air drying, heat drying, and freeze drying. The temperature at the time of firing is 400 to 500 ° C, preferably 450 to 500 ° C.
500 ° C. is suitable, and the time is 2 to 10 hours, preferably 3 to 5 hours.

The shape of the above-mentioned catalyst of the present invention is not particularly limited, and may be any of various shapes used for ordinary catalyst shapes. For example, it is possible to use a four-leaf type or a cylindrical shape. it can. The size of the catalyst of the present invention is usually
1/10 to 1/22 inch is suitable.

The catalyst of the present invention may be used by mixing with a known catalyst or a known inorganic oxide carrier.

The feedstock oil that can be hydrodesulfurized using the catalyst of the present invention includes a straight-run gas oil obtained by atmospheric distillation of crude oil,
Alternatively, cracked gas oil produced from a catalytic cracking device, reduced pressure gas oil obtained by vacuum distillation, and the like are mentioned. In general, the boiling point is 150 to 600 ° C, preferably 200 to 400 ° C,
Those having a sulfur content of 3% by mass or less, preferably 2.5% by mass or less, and a density (15 ° C.) of 0.94 g / cm ³ or less are suitable.

When the catalyst of the present invention is used in a desulfurization apparatus by catalytic hydrogenation on a commercial scale, it is used as a fixed bed, a moving bed or a fluidized bed, into which the gas oil to be desulfurized is introduced, and , Under high pressure (equivalent hydrogen partial pressure)
Perform the desired desulfurization. Most commonly, the catalyst is maintained as a fixed bed such that gas oil passes down through the fixed bed. The catalyst can be used in a single reactor or in several successive reactors. In particular, when the feed oil is relatively heavy light oil, it is preferable to use a multi-stage reactor.

As a preferred example of the reaction, light oil is used at a temperature of about 200 to 500 ° C., more preferably about 250 to 40 ° C.
At 0 ° C., the liquid hourly space velocity is about 0.05 to 5.0 hr ⁻¹ , more preferably about 0.1 to 4.0 hr ⁻¹ , and the hydrogen partial pressure is about 1 to 20 MPa, more preferably about 3 to 10 MPa.
To contact the catalyst.

[0040]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 In an Erlenmeyer flask, 3.9 g of phosphoric acid was dissolved in 75 g of water and stirred to prepare an aqueous solution of phosphoric acid.

In another Erlenmeyer flask, 32.7 g of ammonium molybdate and 1.5 g of tungstic acid were added to water so that the WO ₃ / MoO ₃ ratio in the catalyst, which is the final product of this example, was 0.05. The resulting mixture was dissolved in 75 g, and further, ammonia water was added and stirred until ammonium molybdate and tungstic acid were completely dissolved to prepare a mixed aqueous solution of ammonium molybdate and tungstic acid.

In another Erlenmeyer flask, cobalt nitrate 27
g was dissolved in 75 g of water and stirred to prepare an aqueous solution of cobalt nitrate.

The above phosphoric acid aqueous solution was placed in an eggplant type flask in a specific surface area of 336 m ² / g and a pore volume of 0.71 cc /
g of a γ-alumina carrier having an average pore size of 85 ° was impregnated. The impregnation temperature was normal temperature, and the impregnation time was 1 hour. Then, it is dried (air-dried) and placed in a muffle furnace at 500 ° C.
For 4 hours to complete the first-stage impregnation (impregnation with phosphoric acid aqueous solution).

The mixed catalyst of ammonium molybdate and tungstic acid was impregnated with the catalyst after completion of the first stage impregnation in an eggplant-shaped flask under the same conditions as in the first stage impregnation operation. Dry firing under the same conditions as dry firing,
The second stage impregnation (impregnation with a mixed aqueous solution of molybdenum and tungsten) was completed.

After completion of the second stage impregnation, the catalyst is impregnated with an aqueous solution of cobalt nitrate in an eggplant-shaped flask under the same conditions as in the first stage impregnation operation, and under the same conditions as in the first stage drying and firing. After drying and firing, the third stage of impregnation and loading (impregnation and loading of an aqueous cobalt solution) was completed, and a catalyst A was produced.

Example 2 Example 1 was repeated except that 32.7 g of ammonium molybdate was changed to 16.4 g and 1.5 g of tungstic acid was changed to 0.2 g so that the WO ₃ / MoO ₃ ratio was 0.01.
Catalyst B was produced in the same manner as described above.

Example 3 In order to obtain a WO ₃ / MoO ₃ ratio of 0.20, 32.7 g of ammonium molybdate was changed to 40.9 g, 1.5 g of tungstic acid was changed to 7.5 g, and cobalt nitrate 2 was changed.
Catalyst C was produced in the same manner as in Example 1, except that 7 g of nickel nitrate was used instead of 7 g.

Example 4 A catalyst D was produced in the same manner as in Example 1, except that 1.5 g of tungstic acid was changed to 0.6 g so that the WO ₃ / MoO ₃ ratio became 0.02.

Example 5 A catalyst E was produced in the same manner as in Example 1, except that 1.5 g of tungstic acid was changed to 3.0 g so that the WO ₃ / MoO ₃ ratio became 0.10.

Example 6 In an Erlenmeyer flask, 2.0 g of phosphoric acid, 38.0 g of molybdophosphoric acid, 1.7 g of tungstophosphoric acid, and 24.1 g of cobalt acetate so that the WO ₃ / MoO ₃ ratio becomes 0.05.
g was dissolved in 75 g of water and stirred to prepare a four-component mixed aqueous solution.

The above aqueous solution was impregnated with 100 g of a γ-alumina carrier having a specific surface area of 336 m ² / g, a pore volume of 0.71 cc / g and an average pore diameter of 85 ° in an eggplant type flask. The impregnation temperature was normal temperature, and the impregnation time was 1 hour.
Thereafter, it was dried (air-dried) and calcined in a muffle furnace at 500 ° C. for 4 hours to produce Catalyst F.

Example 7 A catalyst G was produced in the same manner as in Example 6, except that 2.0 g of phosphoric acid was changed to 10.0 g.

Example 8 A catalyst H was produced in the same manner as in Example 6, except that 2.0 g of phosphoric acid was changed to 3.2 g.

Example 9 A catalyst I was produced in the same manner as in Example 6, except that 2.0 g of phosphoric acid was replaced with 6.0 g.

Example 10 A catalyst was prepared in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 1.2 g and 27 g of cobalt nitrate was changed to 16 g so that the WO ₃ / MoO ₃ ratio became 0.04. J was manufactured.

Example 11 A catalyst was prepared in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 2.1 g and 27 g of cobalt nitrate was changed to 38 g so that the WO ₃ / MoO ₃ ratio became 0.07. K was manufactured.

Example 12 1.5 g of tungstic acid was changed to 2.1 g, 27 g of cobalt nitrate was changed to 13 g of cobalt nitrate, and 14 g of nickel nitrate was changed so that the WO ₃ / MoO ₃ ratio became 0.07. Is 241 m ² / g, pore volume 0.75 cc
/ G and a catalyst L were produced in the same manner as in Example 1 except that a γ-alumina support having an average pore diameter of 92A was used.

Comparative Example 1 A catalyst M was produced in the same manner as in Example 1 except that the impregnation with phosphorus was not performed.

Comparative Example 2 A catalyst N was produced in the same manner as in Example 1 except that the impregnation with tungstic acid was not performed.

Comparative Example 3 To 1.5 g of tungstic acid and 3.0 g of phosphoric acid
Was replaced with 20 g by the same method as in Example 1.
Was manufactured.

Comparative Example 4 A catalyst P was produced in the same manner as in Example 1, except that 1.5 g of tungstic acid was changed to 0.15 g so that the WO ₃ / MoO ₃ ratio became 0.005.

Comparative Example 5 A catalyst Q was produced in the same manner as in Example 1, except that 1.5 g of tungstic acid was changed to 7.5 g so that the WO ₃ / MoO ₃ ratio became 0.25.

Comparative Example 6 A catalyst R was produced in the same manner as in Example 1, except that 32.7 g of ammonium molybdate was changed to 13.1 g so that the WO ₃ / MoO ₃ ratio became 0.13.

Comparative Example 7 A catalyst S was produced in the same manner as in Example 1, except that 32.7 g of ammonium molybdate was changed to 49.1 g so that the WO ₃ / MoO ₃ ratio became 0.03.

Comparative Example 8 A method similar to that of Example 1 was used, except that the first impregnation was an aqueous solution of cobalt, the second impregnation was an aqueous solution of molybdenum and tungsten, and the third impregnation was an aqueous solution of phosphorus. Catalyst T
Was manufactured.

Comparative Example 9 The specific surface area was 190 m ² / g and the pore volume was 0.71 cc /
g, a catalyst U was produced in the same manner as in Example 1 except that a γ-alumina support having an average pore diameter of 101 ° was used.

Tables 1 and 2 show the compositions of the catalysts A to U produced in Examples 1 to 12 and Comparative Examples 1 to 9, respectively.

[0069]

[Table 1]

[0070]

[Table 2]

Catalyst A produced in the above Examples and Comparative Examples
Using ~ U, the hydrodesulfurization reaction of light oil was carried out under the reaction conditions shown in Table 3.

[0072]

[Table 3]

The catalyst performance was evaluated by operating under the above reaction conditions, measuring the sulfur content after passing the oil for 100 hours, obtaining the reaction rate constant based on the following equation, and setting the value of the catalyst M to 10%.
The evaluation was performed with a relative evaluation of 0. The results are shown in Table 4.

[0074]

(Equation 1)

[0075]

[Table 4]

[0076]

According to the present invention, the desulfurization specific activity obtained from the rate constant under the reaction conditions can be converted to the conventional catalyst by the synergistic effect of molybdenum, tungsten, tungsten and phosphorus in the same catalyst under the reaction conditions. It can be significantly higher in comparison. As a result, in the present invention, it is possible to produce a fuel oil having a low sulfur content at low cost, for example, by reducing the size of an actual reactor and reducing the amount of a catalyst, which is extremely effective in practical use.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Etsuo Suzuki 1134-2 Gondogendo, Satte City, Saitama Prefecture Cosmo Research Institute, Inc. (72) Inventor Osamu Chiyoda 1134-2 Gongendo Hall, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center (72) Inventor Hitomi Inoue 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center (56) References JP-A-52-13503 (JP, A JP-A-63-123445 (JP, A) JP-A-63-158133 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10G 45/08 C10G 45/50 B01J 27 / 188

Claims (2)

(57) [Claims] 1. An inorganic oxide carrier containing 1 to 10% by mass of cobalt and / or nickel, 1 to 5% by mass of oxide, 1 to 5% by mass of oxide and molybdenum oxidized on a catalyst basis. Tungsten is supported so that the mass ratio of tungsten to molybdenum is 0.01 to 0.20 in terms of oxide, and the average pore diameter of the catalyst is 70 to 80 %. Thus , phosphorus is supported on the inorganic oxide carrier in the first step,
Carries molybdenum and tungsten, and Kovar at the third stage
And / or nickel
Hydrodesulfurization catalyst gas oil characterized by a Rukoto. 2. Cobalt on an inorganic oxide carrier on a catalyst basis.
Oxide and / or nickel
1 to 10% by mass in total, and 1 to 5% by mass of phosphorus in terms of oxide
%, Molybdenum is 10 to 25% by mass in terms of oxide, and
And the mass ratio of tungsten to molybdenum
Carry tungsten so that it becomes 0.01 to 0.20
And the catalyst has an average pore diameter of 70 to 80 °, and the inorganic oxide support contains both cobalt and nickel.
Or one or the other, molybdenum, tungsten, phosphorus
Of light oil, characterized in that water is supported simultaneously in one stage
Sulfurization desulfurization catalyst .